EP0235486A1 - Zweistufenverfahren zur Herstellung von verknüpften Organopolysilazanen mit verbesserten Hitzeeigenschaften und deren Anwendung in der Herstellung von keramischen Materialien - Google Patents
Zweistufenverfahren zur Herstellung von verknüpften Organopolysilazanen mit verbesserten Hitzeeigenschaften und deren Anwendung in der Herstellung von keramischen Materialien Download PDFInfo
- Publication number
- EP0235486A1 EP0235486A1 EP86420290A EP86420290A EP0235486A1 EP 0235486 A1 EP0235486 A1 EP 0235486A1 EP 86420290 A EP86420290 A EP 86420290A EP 86420290 A EP86420290 A EP 86420290A EP 0235486 A1 EP0235486 A1 EP 0235486A1
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- EP
- European Patent Office
- Prior art keywords
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- carried out
- aminolysate
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- Prior art date
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- 238000000034 method Methods 0.000 title claims description 34
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000000919 ceramic Substances 0.000 title abstract description 17
- 239000002243 precursor Substances 0.000 title abstract 2
- 229920001709 polysilazane Polymers 0.000 claims abstract description 33
- 150000001367 organochlorosilanes Chemical class 0.000 claims abstract description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims 1
- -1 amine chloride Chemical class 0.000 abstract description 20
- 238000007098 aminolysis reaction Methods 0.000 abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 1
- FXOCTISBMXDWGP-UHFFFAOYSA-N dichloro(silyl)silane Chemical compound [SiH3][SiH](Cl)Cl FXOCTISBMXDWGP-UHFFFAOYSA-N 0.000 abstract 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 abstract 1
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 238000002411 thermogravimetry Methods 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 12
- 238000000197 pyrolysis Methods 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000005915 ammonolysis reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910008045 Si-Si Inorganic materials 0.000 description 3
- 229910006411 Si—Si Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229940095054 ammoniac Drugs 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- KQHIGRPLCKIXNJ-UHFFFAOYSA-N chloro-methyl-silylsilane Chemical compound C[SiH]([SiH3])Cl KQHIGRPLCKIXNJ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 150000001369 organodichlorosilanes Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HXCKCCRKGXHOBK-UHFFFAOYSA-N cycloheptane Chemical compound [CH]1CCCCCC1 HXCKCCRKGXHOBK-UHFFFAOYSA-N 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 210000002741 palatine tonsil Anatomy 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
Definitions
- Organopolysilazanes hereinafter called polysilazanes
- polysilazanes are well known products in the form of monomers, oligomers and cyclic or linear polymers and also in the form of resinous polymers. These polysilazanes can be prepared by a wide variety of methods from a wide range of starting materials.
- the starting polysilazanes prepared from ammonia are generally called ammonolysates and the starting polysilazanes prepared from an amino compound other than ammonia comprising an NH 2 group are called aminolysates which therefore include ammonolysates.
- These polysilazanes can in particular be shaped and be pyrolyzed in the form of Si 3 N 4 , SiC or their mixtures.
- silicon nitride there is another way which consists in reacting at high temperature and in vapor phase chlorosilanes (SiCl 4 , HSiC13 and H 2 SiC1 2 ) on ammonia. According to this method leading directly to a powdered product, it is difficult to manufacture objects in the form, in particular, of fibers.
- the polysilazanes can be spun into continuous fibers, the pyrolysis of which results in ceramic fibers.
- They can be in the form of more or less thin films, solid molded parts, and can be used as a binder for ceramic fiber or carbon fiber and as a sintering binder for porous ceramic parts.
- the starting aminolysates prepared according to known methods are generally in the form of a liquid of low or high viscosity, or even in a pasty state, going as far as the solid state and they generally contain a content which may be high in species of low molecular mass capable of being eliminated during the pyrolysis and consequently of correspondingly reducing the weight yield of ceramic product brought back to the starting product.
- these aminolysates in particular in the case where they contain a high content of difunctional silicon (for example D N ) are not sufficiently thermally stable during pyrolysis; they degrade by breaking connections: Si - NH or Si - N to give rise to volatile oligomers thereby reducing the weight yield of ceramic product reduced to the starting product.
- D N difunctional silicon
- a method for manufacturing shaped parts such as fibers comprising silicon carbide, silicon nitride or their mixtures with other ceramic products is proposed, by carrying out a first heat treatment at a temperature between 200 and 800 ° C of a polysilazane, in order to obtain a fusible carbosilazane resin which can be spun in the molten state and then pyrolyzed at a temperature between 800 and 2000 ° C.
- the above patent certainly constitutes significant progress, but it has the double disadvantage of requiring a first heat treatment at a temperature which may already be very high (200 - 800 ° C.) and of working a carbosilazane in the molten state under conditions anhydrous and in an inert atmosphere. In addition, the ceramic weight yield may be insufficient.
- US Pat. No. 3,007,886 describes a process for treating polysilazanes with metal salts of monocarboxylic acids soluble in hydrocarbon solvents and US Pat. No. 3,187,030 describes a process for treating polysilazanes with particular metal salts strong inorganic acids, catalysis therefore being ensured by metal cations playing the role of Lewis acid.
- the teaching of these two patents therefore aims at a polymerization reaction by opening a silazane bond.
- the object of the present invention is to propose a simple, effective, economical and easy to use means for preparing in the most diverse forms (wires, molded articles, coatings, films, etc.) polysilazanes which, during their pyrolysis, at a temperature of between 1000 and 2000 ° C., give ceramic products having excellent properties.
- the patterns are distinguished: considered to be monofunctional considered to be dysfunctional considered trifunctional and considered tetrafunctional.
- the functionality f N of the disilyl units is calculated like that of the halodisilanes by considering the nitrogen substituents in place of the halogen atoms.
- the average functionality (f N ) m of the aminolysates is calculated from the molar percentages of the different units composing the aminolysate weighted with their own functionality; thus for n different reasons:
- the method according to the invention suddenly makes it possible to obtain reticulates of polysilazanes having an average functionality (fN) m greater than 2 strictly, generally between 2.1 and 3.0 by presenting in their network silicon nodes of the type T N and / or Q N in sufficient number to ensure better product stability during pyrolysis evaluated by dynamic thermogravimetry (TGA) by pyrolyzing them from room temperature (20 ° C) to 1,400 ° C under nitrogen with a speed temperature rise of 2 ° C / minute.
- TGA dynamic thermogravimetry
- the process of the invention has the advantage to separate the stages of network formation, to have a more homogeneous distribution of the silicon nodes in the network of the reticulate leading to a better yield in ceramics with for example creation of sequences:
- the reaction of the organochlorosilanes or disilanes or of the chlorosilazanes or chlorodisilylsilazanes on the polysilazanes obtained at the end of step 1) is carried out in bulk or in a solvent medium such as, for example, toluene or isopropyl ether, preferably in the presence of a aliphatic tertiary amine such as trimethylamine, triethylamine, an aromatic amine such as pyridine, triazine or their derivatives at a temperature between 0 and 160 ° C in the presence of an amino organic compound carrying at least one NH group 2 , preferably ammonia.
- a solvent medium such as, for example, toluene or isopropyl ether, preferably in the presence of a aliphatic tertiary amine such as trimethylamine, triethylamine, an aromatic amine such as pyridine, triazine or their derivatives at a temperature between 0 and 160
- R may be a hydrogen atom or a saturated aliphatic hydrocarbon radical, preferably having from 1 to 8 carbon atoms, such as a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl radical; the radical R can also be a saturated cyclic hydrocarbon radical having from 3 to 7 carbon atoms such as the cyclopropyl, cyclobutyl, cyclcpentyl, cyclohexyl and cycloheptyl radical; R can be a phenyl or arylalkyl radical such as the benzyl and phenylethyl radicals, or an alkylaryl radical such as the tolyl and xylyl radicals.
- R can also be an aliphatically unsaturated radical preferably having from 2 to 8 carbon atoms; mention may be made of ethynyl, propynyl, etc. radicals, vinyl, allyl radicals, etc. and cycloalkenyl radicals, such as cyclopentenyl, cyclohexenyl, cycloheptenyl and cyclooctenyl radicals.
- the methyl, vinyl and phenyl radicals are the preferred radicals.
- Methyl radicals, vinyl and phenyl are the preferred radicals R.
- organodichlorosilane or organodichlorodisilane which can be used alone or as a mixture during step 1), there may be mentioned:
- the organic groups of the organochlorosilicon compounds linked directly to the silicon atoms which can be used during step 2) can be R groups as above.
- the chlorine atoms of the organochloropolysilazanes or of the organochloropolydisilylsilazanes which can also be used in step 2) are carried by silicon atoms.
- organochlorosilicates from step 2 are used for one mole of organochlorosilanes or organochlorodisilanes from step 1).
- steps 1) and 2) are well known. We can for example cite as reference for step 1) in the case of an organodichlorosilane the British patent GB-A-881,178 and in the case of an organodichlorodisilane the European patent EP-A-75,826.
- a further polymerization of the generally cyclic polysilazane obtained in step 1) is carried out between steps 1 °) and 2 °) using a suitable catalyst used in a catalytically effective amount.
- the silane and / or the disilane used in step 1) is chosen from R 2 SiCl 2 and R 4 Si 2 Cl 2 .
- This homogeneous or heterogeneous polymerization can be carried out in particular by following the teaching of Japanese patent application K OKAI 77/160 446 mentioned above by treatment of acidic earths, for example of the Tonsil® or Actisil® type, or of montmorillonite washed with acid sulfuric, or using a catalyst of the Spherosil ® type formed of a porous mineral support covered with a polymeric film carrying a sulfonic or phosphonic group as for example described in French patent FR-A-2,505,850.
- This polymerization can also be carried out by treatment of the polysilazane with metal salts of monocarboxylic acids soluble in hydrocarbon solvents in accordance with the teaching of US Pat. No. 3,007,886 or with particular metal salts of strong inorganic acids playing the role Lewis acid, according to the teachings of US-A-3,187,030.
- the preferred polymerization catalyst is chosen from HClO 4 and CF 3 SO 3 H.
- This catalyst is generally used at concentrations of between 1 ppm and 10,000 ppm of acid brought back to the starting polysilazane and preferably between 10 ppm and 5,000 ppm.
- the polymerization temperature is between 20 ° C and 180 ° C, preferably between 120 ° C and 160 ° C.
- the reaction can be carried out en masse, which is a clear advantage. It is however possible to use an organic solvent such as toluene, methylene chloride, benzene, xylene, hexane, heptane, etc.
- the reaction can be carried out at atmospheric pressure, under pressure or under reduced pressure.
- the duration of the reaction is of course a function of the catalyst concentration and the reaction temperature. For a temperature between 120 and 160 ° C and an acid concentration between 10 and 5000 ppm, the duration of the polymerization is advantageously between 30 minutes and 30 hours.
- the organopolysilazane composition obtained according to the process of the invention is preferably used without solvent.
- a viscosity at 25 ° C. of between 10 and 5,000 mPa.s, preferably between 100 and 1,000 mPa.s, is chosen.
- compositions for coating or impregnating a support can be used, but it is then necessary, when one wants to use the compositions for coating or impregnating a support, to dissolve the composition in an organic solvent compatible with polysilazanes such as benzene, toluene, hexane, cyclohexane , isopropyl ether, ethyl ether, dichloronethane and chlorobenzene.
- polysilazanes such as benzene, toluene, hexane, cyclohexane , isopropyl ether, ethyl ether, dichloronethane and chlorobenzene.
- viscosities higher than 5000 mPa.s. It is possible to operate without solvent in the molten state or in solution, the crosslinking taking place at the outlet of the die by passage through an oven and / or under radiation (UV, electron beams).
- the polysilazane composition obtained according to the process of the invention may also contain fillers preferably chosen from SiO 2 , Si 3 N 4 , SiC, BN, B203, B 4 C, AlN, Al 2 O 3, Al 4 C 3 , TiN, TiO 2 , TiC, Zr0 2 , ZrC, V0 2 etc .
- Ceramic fibers made in particular of SiC, Si0 2 , Si 3 N 4 , B 4 C etc .
- the supports coated or impregnated with the cured composition, or the fibers can undergo immediately or subsequently a pyrolysis treatment preferably under vacuum or under pressure or under an inert atmosphere with a rise in temperature ranging from the crosslinking temperature to 1500-2 000 ° C, depending on the type of ceramic or binder desired.
- the silazane composition obtained according to the process of the invention therefore makes it possible to make intermediate semi-products which can be stored in ambient air and which can be subsequently pyrolyzed.
- the polysilazanes obtained are analyzed by dynamic thermogramometry (TGA) by pyrolysis of the temperature ambient (20 ° C) to 1400 ° C under nitrogen with a temperature rise rate of 2 ° C / minute.
- TGA yield % by weight of solid residue at 1400 ° C.
- the ammonolysis and coammonolysis reactions are carried out in a first reactor I of 3 liters of cylindrical shape (provided with a double jacket to cool the reaction volume).
- the reactor is topped with a gas condenser.
- Mechanical agitation is ensured by two RUSHTON® turbines (a turbine with straight blades, a turbine with inclined blades) arranged along the agitation shaft.
- the introduction of N 2 and NH 3 gases takes place via a thin tube immersed in the solution so as to reveal NH 3 just under the first stirring turbine.
- the reaction mixture is withdrawn and is introduced into a second reactor II provided with mechanical stirring (RUSHTON® turbine with straight blades) and a filter bed (average porosity 10 ⁇ m).
- the ammonolysates are filtered and the rinsing solvents are introduced into a third 6-liter reactor III provided with a double jacket and mechanical stirring, with a RUSHTON® turbine with straight blades.
- This reactor where the catalytic treatment is optionally carried out between step 1) and step 2) is inerted under N 2 or placed under vacuum (25 mbar).
- the entire installation is placed under an inert atmosphere several hours before handling.
- the entire reaction, ammonolysis, filtration, evaporation of the solvent is carried out under dry nitrogen.
- the products obtained are placed in sealed bottles inerted with nitrogen and stored, weighed and handled in a glove box inerted with nitrogen.
- the polysilazane obtained at the end of step 1 is used as that obtained in a known manner by reaction of dimethyldichlorosilane with ammonia. Hexamethylcyclotrisilazane called is rectified and the fraction with a boiling point of 188 ° C and a melting point of 10 ° C is recovered. It is dried over CaCl2. This has a TGA yield at 1400 ° C close to 0.
- the reaction mixture is heated for two hours at 110 ° C under nitrogen.
- the solution is cooled to 20 ° C. and a stream of NH 3 (5 cm 3 / s) is bubbled for an hour and a half.
- the temperature is maintained at 20 ° C. using a water + ice bath.
- the NH 4 Cl precipitate is removed in reactor II.
- the toluene is removed under vacuum (2 mbar at 70 ° C).
- a slightly yellow viscous and cloudy viscous product is recovered 3,500 mPa.s at 25 ° C with a yield of 74%.
- the TGA yield is 54%.
- the reaction mixture is heated for 2 hours at 60 ° C. under nitrogen. After having cooled the solution to 20 ° C., ammonia (5 cm 3 / s for 1 hour) is bubbled through the solution. The temperature of 20 ° C is maintained using a water + ice bath. After cooling to 0 ° C , the NH 4 Cl precipitate is filtered in reactor II and the toluene is removed under vacuum (2 mbar at 70 ° C), the product is recovered which is a clear oil with a viscosity of 340 mPa.s . The reaction yield is 92%.
- the crosslink has a TGA yield of 58%.
- the TG A yield of the reticulate is 40%. Although equal to the (f N ) m of comparative example 4, the TGA yield of this test is much higher than that of comparative example 4, this indicates a more homogeneous distribution of the trifunctional patterns within the network. polysilazane formed.
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86420290T ATE60344T1 (de) | 1985-11-28 | 1986-11-25 | Zweistufenverfahren zur herstellung von verknuepften organopolysilazanen mit verbesserten hitzeeigenschaften und deren anwendung in der herstellung von keramischen materialien. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8517818A FR2590584B1 (fr) | 1985-11-28 | 1985-11-28 | Procede de preparation, en deux etapes, de reticulats d'organopolysilazanes de tenue thermique amelioree pouvant servir notamment comme precurseur ceramique |
FR8517818 | 1985-11-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0235486A1 true EP0235486A1 (de) | 1987-09-09 |
EP0235486B1 EP0235486B1 (de) | 1991-01-23 |
Family
ID=9325355
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86420290A Expired - Lifetime EP0235486B1 (de) | 1985-11-28 | 1986-11-25 | Zweistufenverfahren zur Herstellung von verknüpften Organopolysilazanen mit verbesserten Hitzeeigenschaften und deren Anwendung in der Herstellung von keramischen Materialien |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0235486B1 (de) |
JP (1) | JPS62156136A (de) |
KR (1) | KR910008328B1 (de) |
AT (1) | ATE60344T1 (de) |
AU (1) | AU586050B2 (de) |
BR (1) | BR8605779A (de) |
DE (1) | DE3677193D1 (de) |
ES (1) | ES2020197B3 (de) |
FR (1) | FR2590584B1 (de) |
GR (1) | GR3001627T3 (de) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0266918A2 (de) * | 1986-11-04 | 1988-05-11 | Dow Corning Corporation | Verfahren zur Herstellung von für die Herstellung von keramischen Materialien geeigneten Polymeren aus cyclischen Silazanen und Halosilanen |
EP0312825A2 (de) * | 1987-10-06 | 1989-04-26 | Hoechst Aktiengesellschaft | Polymere Hydridochlorsilazane und Verfahren zu ihrer Herstellung |
EP0313878A2 (de) * | 1987-10-06 | 1989-05-03 | Hoechst Aktiengesellschaft | Polymere Hydridosilazane und Verfahren zu ihrer Herstellung sowie ihre Verwendung |
EP0321916A2 (de) * | 1987-12-23 | 1989-06-28 | Hoechst Aktiengesellschaft | Polymere Hydridosilazane, Verfahren zu ihrer Herstellung, sowie die Herstellung Siliziumnitrid enthaltender keramischer Materialien |
FR2633301A1 (fr) * | 1988-06-22 | 1989-12-29 | Atochem | Polysilazanes, leur procede de preparation, leur utilisation comme precurseurs de ceramiques et lesdites ceramiques |
EP0351747A2 (de) * | 1988-07-20 | 1990-01-24 | Hoechst Aktiengesellschaft | Verfahren zur Herstelllung von Siliziumnitrid enthaltendem keramischem Material aus polymeren Hydridochlorsilazanen |
FR2635528A1 (fr) * | 1988-08-17 | 1990-02-23 | Atochem | Procede de preparation de polyhydrosilazanes derives d'hydrazine et l'utilisation desdits silazanes comme precurseurs de ceramique |
EP0364338A1 (de) * | 1988-10-14 | 1990-04-18 | Rhone-Poulenc Chimie | Verfahren zur Kontrolle der katalytischen Polymerisation einer Polysilazanzusammensetzung |
EP0372377A2 (de) * | 1988-12-03 | 1990-06-13 | Hoechst Aktiengesellschaft | Polymere ethylenverbrückte Chlorsilazane, Verfahren zu ihrer Herstellung, sowie ein Verfahren zur Herstellung von Siliziumnitrid enthaltenden keramischen Materialien. |
EP0372379A2 (de) * | 1988-12-03 | 1990-06-13 | Hoechst Aktiengesellschaft | Chlorhaltige Silazanpolymere, Verfahren zu ihrer Herstellung, Verfahren zur Herstellung von Siliziumnitrid enthaltenden keramischen Materialien |
EP0375974A2 (de) * | 1988-12-03 | 1990-07-04 | Hoechst Aktiengesellschaft | Polysubstituierte chlorhaltige Silazanpolymere, Verfahren zu ihrer Herstellung, sowie deren Verwendung zur Herstellung Siliziumnitrid enthaltender keramischer Materialien |
EP0383164A2 (de) * | 1989-02-11 | 1990-08-22 | Hoechst Aktiengesellschaft | Hochfeste Verbundkeramik, Verfahren zu ihrer Herstellung sowie ihre Verwendung |
FR2652081A1 (fr) * | 1989-09-21 | 1991-03-22 | Rhone Poulenc Chimie | Procede de preparation d'un composite si3n4-sic. |
FR2653131A1 (fr) * | 1989-10-17 | 1991-04-19 | Rhone Poulenc Chimie | Procede de preparation de polyorganosilazane de masse moleculaire elevee. |
EP0439844A2 (de) * | 1990-01-27 | 1991-08-07 | Hoechst Aktiengesellschaft | SiC1-Gruppen enthaltende Silazanpolymere, Verfahren zu ihrer Herstellung, aus ihnen herstellbare, Siliciumnitrid enthaltende keramische Materialien, sowie deren Herstellung |
WO1992001732A2 (en) * | 1990-07-16 | 1992-02-06 | Ethyl Corporation | Preceramic polysilazane compositions |
EP0572007A1 (de) * | 1992-05-27 | 1993-12-01 | Wacker-Chemie Gmbh | Verfahren zur Herstellung von Polysilazanen |
US6780514B2 (en) | 2001-08-07 | 2004-08-24 | Nippon Electric Glass Co., Ltd. | Optical communication device substrate and optical communication device |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2590580B1 (fr) * | 1985-11-28 | 1988-05-13 | Rhone Poulenc Spec Chim | Procede de traitement catalytique d'un polysilazane comportant en moyenne au moins deux groupes hydrocarbone a insaturation aliphatique par molecule |
JPS62199623A (ja) * | 1986-02-28 | 1987-09-03 | Toshiba Silicone Co Ltd | 環状ポリメチルシラザン構造を有する重合体の製造方法 |
DE3639511A1 (de) * | 1986-11-20 | 1988-06-01 | Wacker Chemie Gmbh | Verfahren zur herstellung von silazanpolymeren |
CA1302619C (en) * | 1987-06-08 | 1992-06-02 | Gary Thomas Burns | Silane modified polysilacyclobutasilazanes |
FR2616436B1 (fr) * | 1987-06-10 | 1989-12-29 | Europ Propulsion | Copolymeres a liaisons si-n et si-si, polycarbosilazanes obtenus par pyrolyse desdits copolymeres et utilisation desdits polycarbosilazanes pour la preparation de carbonitrure de silicium |
US4772516A (en) * | 1987-11-09 | 1988-09-20 | Mahone Louis G | Stable methylpolydisilylazane polymers |
FR2640981B1 (de) * | 1988-12-23 | 1991-03-01 | Rhone Poulenc Chimie | |
CN106232687B (zh) * | 2014-04-24 | 2020-07-07 | Az电子材料(卢森堡)有限公司 | 共聚聚硅氮烷、其制造方法以及包含其的组合物以及使用了其的二氧化硅质膜的形成方法 |
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US3036019A (en) * | 1958-11-03 | 1962-05-22 | Richardson Co | Modification of silicon-nitrogen containing compounds |
FR2140123A1 (de) * | 1971-06-01 | 1973-01-12 | Dow Corning | |
US4312970A (en) * | 1981-02-20 | 1982-01-26 | Dow Corning Corporation | Silazane polymers from {R'3 Si}2 NH and organochlorosilanes |
US4404153A (en) * | 1981-01-15 | 1983-09-13 | Dow Corning Corporation | Process for the preparation of poly(disilyl)silazane polymers and the polymers therefrom |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2590580B1 (fr) * | 1985-11-28 | 1988-05-13 | Rhone Poulenc Spec Chim | Procede de traitement catalytique d'un polysilazane comportant en moyenne au moins deux groupes hydrocarbone a insaturation aliphatique par molecule |
-
1985
- 1985-11-28 FR FR8517818A patent/FR2590584B1/fr not_active Expired
-
1986
- 1986-11-25 AT AT86420290T patent/ATE60344T1/de not_active IP Right Cessation
- 1986-11-25 EP EP86420290A patent/EP0235486B1/de not_active Expired - Lifetime
- 1986-11-25 ES ES86420290T patent/ES2020197B3/es not_active Expired - Lifetime
- 1986-11-25 BR BR8605779A patent/BR8605779A/pt unknown
- 1986-11-25 DE DE8686420290T patent/DE3677193D1/de not_active Expired - Fee Related
- 1986-11-26 AU AU65687/86A patent/AU586050B2/en not_active Ceased
- 1986-11-27 JP JP61280943A patent/JPS62156136A/ja active Granted
- 1986-11-27 KR KR1019860010071A patent/KR910008328B1/ko not_active IP Right Cessation
-
1991
- 1991-03-20 GR GR91400350T patent/GR3001627T3/el unknown
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US3036019A (en) * | 1958-11-03 | 1962-05-22 | Richardson Co | Modification of silicon-nitrogen containing compounds |
FR2140123A1 (de) * | 1971-06-01 | 1973-01-12 | Dow Corning | |
US4404153A (en) * | 1981-01-15 | 1983-09-13 | Dow Corning Corporation | Process for the preparation of poly(disilyl)silazane polymers and the polymers therefrom |
US4312970A (en) * | 1981-02-20 | 1982-01-26 | Dow Corning Corporation | Silazane polymers from {R'3 Si}2 NH and organochlorosilanes |
Cited By (38)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0266918B1 (de) * | 1986-11-04 | 1994-03-09 | Dow Corning Corporation | Verfahren zur Herstellung von für die Herstellung von keramischen Materialien geeigneten Polymeren aus cyclischen Silazanen und Halosilanen |
EP0266918A2 (de) * | 1986-11-04 | 1988-05-11 | Dow Corning Corporation | Verfahren zur Herstellung von für die Herstellung von keramischen Materialien geeigneten Polymeren aus cyclischen Silazanen und Halosilanen |
US5066623A (en) * | 1987-10-06 | 1991-11-19 | Hoechst Aktiengesellschaft | Polymeric hydridosilazanes and processes for their preparation, and their use |
US5008423A (en) * | 1987-10-06 | 1991-04-16 | Hoechst Aktiengesellschaft | Polymeric hydridochlorosilazanes and processes for their preparation |
EP0312825A2 (de) * | 1987-10-06 | 1989-04-26 | Hoechst Aktiengesellschaft | Polymere Hydridochlorsilazane und Verfahren zu ihrer Herstellung |
EP0313878A2 (de) * | 1987-10-06 | 1989-05-03 | Hoechst Aktiengesellschaft | Polymere Hydridosilazane und Verfahren zu ihrer Herstellung sowie ihre Verwendung |
EP0313878A3 (en) * | 1987-10-06 | 1990-04-25 | Hoechst Aktiengesellschaft | Polymeric hydridosilazanes, process for their preparation and their use |
EP0312825A3 (en) * | 1987-10-06 | 1990-04-25 | Hoechst Aktiengesellschaft | Polymeric hydridochlorosilazanes and process for their preparation |
EP0321916A2 (de) * | 1987-12-23 | 1989-06-28 | Hoechst Aktiengesellschaft | Polymere Hydridosilazane, Verfahren zu ihrer Herstellung, sowie die Herstellung Siliziumnitrid enthaltender keramischer Materialien |
EP0321916A3 (en) * | 1987-12-23 | 1990-10-17 | Hoechst Aktiengesellschaft | Polymeric hydridothiosilazanes, process for their preparation, silicon nitride-containing ceramic materials obtainable from them and preparation of these materials |
EP0351262A1 (de) * | 1988-06-22 | 1990-01-17 | Elf Atochem S.A. | Polysilazane, ihre Herstellung und Anwendung zur Herstellung von keramischen Materialien und die keramischen Materialien |
FR2633301A1 (fr) * | 1988-06-22 | 1989-12-29 | Atochem | Polysilazanes, leur procede de preparation, leur utilisation comme precurseurs de ceramiques et lesdites ceramiques |
EP0351747A2 (de) * | 1988-07-20 | 1990-01-24 | Hoechst Aktiengesellschaft | Verfahren zur Herstelllung von Siliziumnitrid enthaltendem keramischem Material aus polymeren Hydridochlorsilazanen |
US5075266A (en) * | 1988-07-20 | 1991-12-24 | Hoechst Aktiengesellschaft | Process for the production of ceramic material containing silicon nitride from polymeric hydridochlorosilazanes |
EP0351747A3 (de) * | 1988-07-20 | 1991-01-23 | Hoechst Aktiengesellschaft | Verfahren zur Herstelllung von Siliziumnitrid enthaltendem keramischem Material aus polymeren Hydridochlorsilazanen |
EP0359604A1 (de) * | 1988-08-17 | 1990-03-21 | Elf Atochem S.A. | Verfahren zur Herstellung von Polyhydrosilazanen auf der Basis von Hydrazin und deren Anwendung als Ausgangsmaterial für Keramik |
FR2635528A1 (fr) * | 1988-08-17 | 1990-02-23 | Atochem | Procede de preparation de polyhydrosilazanes derives d'hydrazine et l'utilisation desdits silazanes comme precurseurs de ceramique |
EP0364338A1 (de) * | 1988-10-14 | 1990-04-18 | Rhone-Poulenc Chimie | Verfahren zur Kontrolle der katalytischen Polymerisation einer Polysilazanzusammensetzung |
FR2638753A1 (de) * | 1988-10-14 | 1990-05-11 | Rhone Poulenc Chimie | |
US5017640A (en) * | 1988-10-14 | 1991-05-21 | Rhone-Poulenc Chimie | Controlled polymerization of silazane monomers |
EP0375974A3 (de) * | 1988-12-03 | 1991-01-16 | Hoechst Aktiengesellschaft | Polysubstituierte chlorhaltige Silazanpolymere, Verfahren zu ihrer Herstellung, sowie deren Verwendung zur Herstellung Siliziumnitrid enthaltender keramischer Materialien |
EP0372377A2 (de) * | 1988-12-03 | 1990-06-13 | Hoechst Aktiengesellschaft | Polymere ethylenverbrückte Chlorsilazane, Verfahren zu ihrer Herstellung, sowie ein Verfahren zur Herstellung von Siliziumnitrid enthaltenden keramischen Materialien. |
EP0372379A3 (de) * | 1988-12-03 | 1991-04-17 | Hoechst Aktiengesellschaft | Chlorhaltige Silazanpolymere, Verfahren zu ihrer Herstellung, Verfahren zur Herstellung von Siliziumnitrid enthaltenden keramischen Materialien |
EP0372377A3 (de) * | 1988-12-03 | 1991-04-17 | Hoechst Aktiengesellschaft | Polymere ethylenverbrückte Chlorsilazane, Verfahren zu ihrer Herstellung, sowie ein Verfahren zur Herstellung von Siliziumnitrid enthaltenden keramischen Materialien. |
EP0375974A2 (de) * | 1988-12-03 | 1990-07-04 | Hoechst Aktiengesellschaft | Polysubstituierte chlorhaltige Silazanpolymere, Verfahren zu ihrer Herstellung, sowie deren Verwendung zur Herstellung Siliziumnitrid enthaltender keramischer Materialien |
EP0372379A2 (de) * | 1988-12-03 | 1990-06-13 | Hoechst Aktiengesellschaft | Chlorhaltige Silazanpolymere, Verfahren zu ihrer Herstellung, Verfahren zur Herstellung von Siliziumnitrid enthaltenden keramischen Materialien |
EP0383164A2 (de) * | 1989-02-11 | 1990-08-22 | Hoechst Aktiengesellschaft | Hochfeste Verbundkeramik, Verfahren zu ihrer Herstellung sowie ihre Verwendung |
EP0383164A3 (de) * | 1989-02-11 | 1991-03-27 | Hoechst Aktiengesellschaft | Hochfeste Verbundkeramik, Verfahren zu ihrer Herstellung sowie ihre Verwendung |
EP0420714A1 (de) * | 1989-09-21 | 1991-04-03 | Rhone-Poulenc Chimie | Verfahren zur Herstellung eines Verbundwerkstoffes aus Siliciumcarbid und Siliciumnitrid |
FR2652081A1 (fr) * | 1989-09-21 | 1991-03-22 | Rhone Poulenc Chimie | Procede de preparation d'un composite si3n4-sic. |
FR2653131A1 (fr) * | 1989-10-17 | 1991-04-19 | Rhone Poulenc Chimie | Procede de preparation de polyorganosilazane de masse moleculaire elevee. |
EP0424279A1 (de) * | 1989-10-17 | 1991-04-24 | Rhone-Poulenc Chimie | Verfahren zur Herstellung von Polyorganosilazanen mit hohem Molekulargewicht |
EP0439844A2 (de) * | 1990-01-27 | 1991-08-07 | Hoechst Aktiengesellschaft | SiC1-Gruppen enthaltende Silazanpolymere, Verfahren zu ihrer Herstellung, aus ihnen herstellbare, Siliciumnitrid enthaltende keramische Materialien, sowie deren Herstellung |
EP0439844A3 (en) * | 1990-01-27 | 1993-03-10 | Hoechst Aktiengesellschaft | Silazane polymers containing sicl groups, process for preparing them, ceramic materials containing silicon nitrite which can be prepared therefrom, and the preparation of these materials |
WO1992001732A3 (en) * | 1990-07-16 | 1992-03-05 | Ethyl Corp | Preceramic polysilazane compositions |
WO1992001732A2 (en) * | 1990-07-16 | 1992-02-06 | Ethyl Corporation | Preceramic polysilazane compositions |
EP0572007A1 (de) * | 1992-05-27 | 1993-12-01 | Wacker-Chemie Gmbh | Verfahren zur Herstellung von Polysilazanen |
US6780514B2 (en) | 2001-08-07 | 2004-08-24 | Nippon Electric Glass Co., Ltd. | Optical communication device substrate and optical communication device |
Also Published As
Publication number | Publication date |
---|---|
FR2590584A1 (fr) | 1987-05-29 |
ES2020197B3 (es) | 1991-08-01 |
DE3677193D1 (de) | 1991-02-28 |
BR8605779A (pt) | 1987-08-25 |
ATE60344T1 (de) | 1991-02-15 |
KR870005030A (ko) | 1987-06-04 |
AU586050B2 (en) | 1989-06-29 |
EP0235486B1 (de) | 1991-01-23 |
KR910008328B1 (ko) | 1991-10-12 |
JPS62156136A (ja) | 1987-07-11 |
GR3001627T3 (en) | 1992-11-23 |
AU6568786A (en) | 1987-06-04 |
FR2590584B1 (fr) | 1988-03-04 |
JPS6310174B2 (de) | 1988-03-04 |
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